Calcium-magnesium chloride and method of making same



March 17, 1931.- v v. R. COLLINGS ET AL 1,795,835

CALCIUM MAGNESIUM CHLORIDE AND METHOD -OF MAKING SAME Original Filed March 7, 1928 2 sheets sheet 2 FEED HIE/NE (M 0 clcl jsoLur/o/v //v WHICH MOLECULAR RATIO OF g-, LIES BETWEEN 0.50 AND ZERO 0a A P525 Cal-cl BEINE,

1 WATER VA POE EVA POI? A T0 2, SOLUTION SATURATED WITH RESPECT m M C/ -ZCaC/ 'H 0 AND 61C]; ZH O 53' T0 APPROXIMATELY I77 0,

CEYSTA L5 AND MOTHER LIQUOR MOTHER UQUOIZ SAW/RA TED SAME/15 SOLUTION IN E VA PORA TOR PRODUCT CQ L Am: W A5 A MECHANICAL MIXTURE 0F M C/ 2 Ca C/ 6 H 0 AND CaC/ 2 H 0 7TJT'AL, I) C! nvcLuo/lva Apr/sews CEYSTALS IN WHICH RATIO OF L.

OT rs SAME AS //v FEED BIZ/NE z M HER Fig.3

INVENTORS (Jilliam P. Collin 5 BY J'o/m 155G111.

AQTORNEYS f Patented Mar. 17, 1931 warren stares PATENT orrics WILLIAM R. COLLINGS AND JOHN J. SHAFER, 'OF MIDLAND, MICHIGAN, ASSIGNOR-S TO THE DOW CHEMICAL COMPANY, OF MIDLAND, JHICHIGAN, A CORPORATION OF MICHIGAN CALCIUM-MAGNESIUM CHLORIDE AND METHOD 'OF MAKING SAME Original application filed March 7, 1928, Serial No. 259,869, now Patent No. 1,738,492. Divided and this application filed November 4, 1929. Serial No. 404,529. 7

The present improvements relate more particularly to a method of crystallizing from solutions saturated wlth hydrated metall c chlorldes, and speclfically chlorides of cal- 1 cium and magnesium, a product containing -magnesium chloride in solution together.

As a step in such treatment, the separation of sodium chloride or common salt has long been practiced according to well known methods, and one approved method for the recovery and separation from the residual brine of calcium chloride and magnesium chloride, were thus found present in solution together, is disclosed and claimed in U. S. Letters Patent No. 1,627,068 to A. K.

Smith and C. F. Prutton, dated May 8, 1927.

However, in all such processes there still remains a residual mother liquor that contains the chlorides in question in varying amounts.

One object of thepresent improved process, accordingly, is to enable the working up of such end liquor at any stage in the general process of treating brines of the type in question where the separation of the individual chlorides is discontinued, whether for commercial or other reasons.

A further object is to obtain a product consisting of a mixture of such calcium and magnesium chlorides in the form of a free pouring, noncaking, granular mechan cal mixture of their hydrated chlorides in a wlde range of ratios corresponding to thatof the end liquors utilized in the process. This noncaking, free pouring condition 1s preferably obtained by superficially drying such product in accordance with U. S. Letters Patent No. 1,597,121 to P. Cottringer and lV. Collings, dated February 17, 1925, but, if desired, the drying step may be carried further and to any desired extent for the purpose of standardizing the content of anhydrouschlorides present in the product at such per centage as may be desired, e. g., 75 per cent., 80 per cent., etc. Accordingly, although the ratio of the two chlorides in the product may vary from time to time with a varying ratio thereof present in the available end liquor, which constitutes the feed brine for the process, nevertheless the anhydrous content of the product may be held at a constantfigure for the purpose of yielding a standardized quality of mixed product.

To the accomplishment'of the foregoing and related ends, the invention, then, consists of the steps and product hereinafter fully described and particularly pointed out in the claims, the annexed drawing and the following description setting forth in detail several approved modes of carrying out. the process and corresponding modifications in the product obtained, such disclosed modes and products, however, representing'but several of the various ways in which the principle of the invention may be used.

In said annexed drawing Fig. 1 is a diagrammatic representation, somewhat on the orderof a flow sheet,.showing in proper sequence the principal steps involved in carrying out one form of our improved method or process; and Figs. 2 and 3 are similar flow sheets or diagrams illustrating modifications in such method or process.

Briefly stated, our improved process involves treating a brine containing calcium and magnesium chlorides in any ratio of MgCl 031012 MgCl 031012 is the same as that in the feed brine, and the salts'so obtained may be thereupon dried in a current of hot gases without melting.

Several hydrated chlorides and double chlorides'may be separated from CaGl -MgCl liquors depending on temperatures and mother liquor concentrations used. Thus some of the hydrated chlorides which may be separated to obtain the above mentioned ob ject are: magnesium chloride hexahydrate, Mgcl fiH tachydrite,

a new compound represented by the formula, MgChECaCLfil-LO: and calcium chloride dihydrate, (laCl 2l-LO. By variously oombining and proportioning the above mentioned salts, it is possible to obtain a mixture having any deslred molecular ratio of rate out of solution. If the said solid phase,

or phases, be continuously removed by a filter and the mother liquor continuously returned to the evaporator with the feed brine, the analysis of the mother liquor in the evaporatorwill approach and finally approximate a constant analysis. From this point on, the mother liquor analysis in the evaporator does not change substantially, the feed brine merely'enters the evaporator, water is removed as vapor and the balance of the feed is re moved asv a mixture of hydrated chlorides and adhering mother liquor. 'This mixture may then be dried, as by hot air in a dryer, such as a dryer of the rotary kiln or shelf type, to obtain a dried, non-caking free flow mg crystalline mixture suitable for applying to roads for dust prevention purposes, or other use.

In general, it is not important just what hydrates come out as the solid phase in the evaporator, when evaporating brine and returning the mother liquor separated from the crystals to the exaporator. The chief advantageous characteristics of the crystals, or crystal mixture, so obtained are, easy separation from the mother liquor and capacity for drying by hot gases without melting or ballup. F or the above reason, the salting out temperature in the evaporator is best kept low by maintaining a high vacuum on the evaporator so as to make the crystal mixture obtained most easily separable from the mother liquor.

T he three figures in the drawing, as stated, illustrate three different modificationsof our method, or, more specifically, they show three specific ranges for feed brine composition and evaporator temperature, for each of which the particular hydrated end products thereby obtained are indicated.

Thus, assuming a brine to contain CaCl Mgcl NaCl, and H 0 in which the molecular ratio of is less than 2 to 1, the preferred method 0 operation is illustrated in Fig. 1 and would be as follows Evaporate the brine under vacuum to a concentration of approximately 40 B. and separate the 40 B. liquor from the salt, which is practically insoluble in this strength liquor. The (lacl lvlgcl liquor is then fed to a salting evaporator, operating under high vacuum (say 1 mercury absolute pressure), in which water is removed as vapor and a thick crystal slurry of easy pumping consistency is obtained. This slurry is then pumped to a rotary suction filter which separates the mother liquor quite completely from the crystals. The crystals from the filter are handled as hereinafter described while the mother liquor is returned to the evaporator along with the feed liquor. After a certain period of operation the mother liquor in the evaporator will reach and remain at a constant composition of approximately 6% MgCl 53% CaCl and 41% H O corresponding to a molecular ratio of .132 mole MgCl 1.0 mole CaCl and 4.77 mole H O 1.0 mole Oacl This mother liquor is saturated with tachydrite (QMgCl CaCI lQH O) and CaCl 2H O MgCl C 31012 equal to that in the feed liquor, unless the feed liquor happens to have the same MgOl OaOl,

ratio as that of the equilibrium mother liquor in the evaporator. However, after the equilibrium mother liquor concentration has een attained the proportions of caonerno, QMgChCaChlQELO,

and adhering mother liquor coming off the rotary suction filter will be such as to give a K Au total analysis (.132MgCl .CaCl .4.8H O),

the

ratio of which is identical with that of the feed. It is obvious that, if the ratio in the feed liquor is nearly the same as that in the equilibrium mother liquor, the proportion of CaChiZI-LO or of QMgChfiaChlQI-LO may be zero, and that the material being removed by the rotary suction filter will consist of one of the above named hydrates and the adhering mother liquor in such proportion as to give a total analysis of identical Mg'clz CaCl ratio with that of the feed liquor.

After equilibrium conditions have been attained they may be maintained as in customary manner by suitably controlling the heat in-put to the evaporator or the rate of feed or both.

The damp crystals obtained from the rotary suction filter are then dried preferably in a current of hot gases in a rotary dryer to dry up the adhering mother liquor and surface dry the crystals to give a free flowing practically non-caking product.

In the modified method illustrated in Fig. 2, the ratio of magnesium chloride to calcium chloride in the feed brine may range from 2.00 to 0.50 and in such case, if the evaporation be carried on at a temperature from 98 degrees to 152 degrees (1., the liquor in the evaporator will become saturated with taccovered by us in this connection, represented two chlorides in the same ratio as they are present in the feed brine.

Referring to the further modification in our method or process illustrated in Fig. 3, the feed liquor here employed contains magnesium chloride and calcium chloride in a ratio lying between .43 and 0. Upon carrying out the evaporation of this liquor at a temperature between 93 degrees and 177 degrees Q, the solution in the evaporator becomes saturated with respect to the before mentioned new hydrated salt,

MgChECaChfiliO and CaChEHfl),

so that crystals of these salts separate out and form a product in which the ratio of the total magnesium chloride to the total calcium chloride is the same as in the feed brine just as before.

F or any composition of feed liquor, there are one or more temperature ranges in which the above described process is operable for producing a. product having the same Carola ratio as that of the feed. Thus in some cases a feed brine of a given analyses may be worked up to a product of the-same ratio by two different ways, that is by saltin g out two combinations of different hydrated chlorides. These various possibilities, together with one set of operating conditions suitable for working up any CaCl -ldgGl brine, are given in summary form in the following table which shows the general feed composition ranges, temperature ranges, components of product, and specific temperature, pressure and equilibrium mother liquor composition the 'efor, for one mode of working the process in all feed ranges, viz

by the formula MgChQCaChbl-LO. These two hydrated crystalline salts may be separated out in the same manner as describec in connection with the first method and the resulting product, as before, Will contain the Sample approximate operating Approx conditions operable range of Solid phases salting out i. e. components molecular Operable temper- Approximate product MgClz ature range Absolute equilibrium oaou Tam pressure motherliqlwr m feed tto inches p s g evapora, or Hg g 2 moles Gaol:

2MgClz.CaCl-z.12H20 plus OaGlgJZHgO pre- 2 M viously described. 1 to 1 Below 930 l 1.00

MgOlz.2CaClg.6HzO plus 2M"Olg.CaOlz. l 3 145 121120 b 1 to 1 Above 93 0. 120C. 10" L00 .5 O .038 MgOhiGaOlaGHzO plus Gac1 .2H o. T t0 f Above 93 C. 130 C 12" T66" It may be observed that while according to the process of U. S. Patent 1,627,068 crystalline double salts of magnesium and calcium are produced for the purpose of increasing the ratio of the magnesium to calcium therein,

and magnesium chloride, or calcium chloride, is finally separated therefrom' as a single chloride, we produce mixtures of different double salts or mixtures of different hydrated salts, and then convert these into dried granular or crystalline products containing the mixed chlorides of magnesium and calcium in any desired ratio, e. g., in that ratio in which they may exist or may be available in the brine or mother liquor source.

From the foregoing exemplifications of the process, it will accordingly be seen that the latter enables the working up of brine ranging from a pure calcium chloride brine to one in which the ratio of magnesium chloride to calcium chloride is as high as 2.00. Correspondingly, the crystalline product obtained will range from calcium chloride di-hydrate to a mixture of hydrated salts of the single and double chlorides indicated.

Furthermore, the product throughout this entire range of chloride mixture, it will be seen, is a mechanical mixture of hydrated single or double chlorides in granular form, which, upon superficial drying, constitutes a free pouring, non-caking, hygroscopic, granular product having very desirable proper ties. In short, our new process admirably solves the question of how to utilize and work up advantageously the mother liquors remaining from the production of pure magnesium chloride and/or pure calcium chloride, or both, from brines or liquors in which such chlorides are present in solution together. The recovery or separation of these purse salts may be carried out to any desired extent without degard to the ratio in which they are left present in the residual solution or mother liquor since the latter by means of the present process may be converted into the form of the mixed granular hydrated single or double chlorides, or both, as hereinbefore set forth.

The aforesaid hydrated salt mixtures we have found more easily separated by filtration or draining at all temperature ranges in the first method (Fig. 1) and at the lower temperature ranges in the second method (Fig. 2). Indeed they may be even centrifuged without the drawback of caking to a solid mass and they may be readily separated upon a rotary suction filter in a continuous manner corresponding with the approximate rate in which the salts are formed in the evaporator.

The process, accordingly, lends itself admirably for continuous operation, employing an evaporator under reduced pressure and temperature control with continuous feed, continuous withdrawal of mother liquid and crystals, continuous separation on a filter with production of a continuous stream of product in moist, granular form and alike continuous stream of mother liquor for return to the evaporator. Moreover, the crystalline product thus separated may, if desired. be dried in a continuous drier.

This application is a division of our Patent 1,738,492, application filed Mar. 7, 1928.

Other forms of applying the principle of our invention may be employed instead of the ones here explainech change being made in the method or composition, provided the steps or ingredients stated by any of the following claims or the equivalent of such stated steps or ingredients be employed.

We therefore particularly point out and distinctly claim as our invention 1. In a method of making a product of the character described, the steps which consist in adding a solution containing a mixture of calcium and magnesium chlorides to a mother liquor saturated with respect to the hydrated double chloride, MgCl .2CaCl .6I-I O, and calcium chloride dihydra-te, the molecular ratio of magnesium chloride to calcium chloride in such acded solution lying between 0.50 and 0, and simultaneously evaporating such mother liquor to maintain the same approximately at such point of saturation.

2. In a method of making a product of the character described, the steps which consist in adding a solution containing a mixture of calcium and magnesium chlorides to a mother liquor saturated with respect to the hydrated double chloride, MgChQCaChBILO, and calcium chloride dihydrate, the molecular ratio of magnesium chloride to calcium chloride in such added solution lying between 0.5 and 0, and simultaneously evaporating such mother liquor at a temperature between 152 and 177 (1., whereby such mother liquor is iaintained approximately at such point of saturation.

3. As a new article of manufacture, a free flowing, non-calring mixture of hydrated chlorides of magnesium and calcium precipitated as crystals of the hydrated double chloride, MgCl .2CaCl .6H O, and calcium chloride dihydrated from a solution saturated with respect to such chlorides, such crystals being superficially dehydrated to the point where their tendency to cake together in the package is reduced.

Si ned by us this 31st day of October, 1929.

WILLIAM R. COLLINGS. JOHN J. SHAFER. 

